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Publication numberUS2978339 A
Publication typeGrant
Publication dateApr 4, 1961
Filing dateOct 22, 1957
Priority dateOct 22, 1957
Also published asDE1246179B, DE1266459B, US2978340, US3030215, US3129086
Publication numberUS 2978339 A, US 2978339A, US-A-2978339, US2978339 A, US2978339A
InventorsVeatch Franklin, Harvey E Alford, Richard D Croft
Original AssigneeStandard Oil Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Method of producing hollow glass spheres
US 2978339 A
Abstract  available in
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

April 4, 1961 F. VEATCH ETAL 2,978,339

METHOD OF PRODUCING HOLLOW GLASS SPHERES Filed Oct. 22, 1957 s'sneets-sheet 1 I3 I4 27 29 FIG. I

/ 42 l E 46 a2 33 as I6 III: j


I I HARVEY E. ALFORD & GAS-a- -4 RICHARD D. CR FT cooLAm I, BY W .39 R a ATT NEY Aprll 4, 1961 F. VEATCH ETAL 2,978,339

METHOD OF PRODUCING HOLLOW GLASS SPHERES Filed Oct. 22, 1957 3 Sheets-Sheet 2 a 44 45 Q g g 45 4s GAS- 7 AIR :4

4l as Awe FEED 27 u I 56 I5 V 4 I 71 32 a4 -6 I Q 76 J 5 I 7 7 8O INVENTORS FRANKLIN VEATCH HARVEY E. ALFORIj a RICHARD D. CROFT V April 4, 1961 F. VEATCH EI'AL 2,978,339

METHOD OF PRODUCING HOLLOW GLASS SPHERES Filed Oct. 22, 1957 s Sheets-Sheet :5


76 HARVEY E. ALFORD a RI HARD D 0 FT WE BY ATT RNEY United States Patent ice METHOD OF PRODUCING HOLLOW GLASS SPHERES Franklin Veatch, Lyndhurst, Harvey E. Alford, Amherst,

and Richard D. Croft, Wapakoneta, Ohio, assignors to The Standard Oil Corn an Clev l d Ohi ration of Ohio P y, e an 0, a corpo) Filed Oct. 22, 1957, Ser. No. 691,725

3 Claims. (Cl. 106-40) This invention relates to an improved method for producing hollow particles from film-forming materials.

a A process for forming the same general type of hollow particles is disclosed in, Patent No. 2,797,201. In that process a solution Comprising a film-forming material and a latent gas material dissolved in a volatile solvent is subdivided into droplets at the top of a spraying atmosphere, during which the solvent is evaporated and a hole-free, tough surface skin is formed on the particles simultaneously with the liberation of a gas from the latent gas material. V

drying chamber. The droplets then fall through the dry- Patent No. 2,676,892 describes another processin which particles of naturally occurring clay are fed into the top ofa furnace. They expand as they pass downwardly therethrough and are collected at the bottom of the furnace. i I

These previously known methods for producing hol:

conversion to the hollow form approaches the cube of Pi particle diameter, and hence significantly higher beatlrequirements are necessary as particle size increases. Therefore, care must be taken with theseprior art methods to maintain the feed a narrowpartiele size range in order to produce, lowdensity hollow spheres in high yield. If closecontrolof the particle siz e ra nge is not maintained, the larger particleswill pass downward through the furnace too fr apidly due {to their greater mass and result in an underl eated and. poorly expanded product. The converse will be true-of the 7731. smaller particles since due. .to their light weight they .will require a longer time to pass downwardthrough the furnace andresult in.overheated,product a It a be v ed t at h s O e hea i an sl r.

heating of the -film-formingparticles, adverselvaifects product quality in that'it increases bulk density of the product, thereby limitiug the commercial utility ofthe produce} lthas been observedlthat overheated par,- 7

.l .1$ appear eitheras solidspheres or hollow spheres th 11 ver h s xwa wi h a qus u h e y 5 T ind at rauisl ap ar ep masses wh s exhibit intercellular character. Obviously. eitheijsof these forms. in any appreciable percentage fect 'the bulkdensity of the product.

will adversely af- Hence, it is an ob ect of 'this nvention; to provide agnietliod for pbtaining fan improved 1 conversion of film- 'for rningflfeedjjqartiles to hollow spheres; thereby pro whiphis fired directly through the furnace wall} Figure 7 is 11 Ratented Apr. 4, 1961 It is a further object of this invention to provide a method which compensates for variances in the particle size of any selected film-forming material, thereby permitting wider range in the size of the feed particles and effecting savings in classifying and reducing waste.

The principal distinction of the process of the, in .vention over previous methodsresides in the introduction of feed near the bottom of said furnace into an ascending column of hot furnace gases. The feed material is admitted in subdivided form and is entrained in an upward moving, hot, gaseous stream. Actual residence time of the particles within the furnace by this method becomes a function of the particles mass balanced against the buoyancy supplied by the velocity of the upward flow of gases. Therefore, the large particles ascend throughthe hot zone of the furnace more slowly than small particles due to the force of gravity acting on the particles, as may be seen from the earlier discussion (i.e., Stokes law). As a result, the particles ,are heated for a time period in the furnace in direct relationship to the heat requirements necessary to convert the particles of feed into hollow spheres.

Furthermore, this method takes advantage of the inherent property associated with product conversion, and ,it will be seen that this process will utilize this conver sion of feed particles into hollow spheres to better approach the conditions of an ideal furnace. ready been discussed, the ideal operating conditions for the furnace would retain the feed particles within the hot zone=for a residence time just adequate to fusea tough outer skin on the particleandconvert,substantially allthelatent gas "material into a' ga so that coincident with the fusing of the. outershell of theparticle the gas is available to fill the hollow space formed in the interior ofthe particle. It then becomes essential that the hollow sphere is removed from the hot zone of the furnace at the point of its maximum expansion and beof: thefhot zone of thefurnace into regions'of progresr sjiyely'dirninishing' Itemperatureswhere it ,can be retained in 'r'e gionswhere the temperature is below the" fusing temperature of the "feed material so the outerskinbfthe "particle can cool and solidify,providingthe. mechanical ..OtherIimportant-adyantages and features of process, will.,-become fapparent from the following. detailed description of the apparatus and possible modifications erein,

strengtlrldesired priorftoflproduct recovery.

The accompanyingi'jdfawings illustrate func" tional. forms ,of'our' invention and in these drawings; I i -I Figurelis anelevation, partly in section, of an apparatussuitable for carryirig out the method of my invention; fliigurez is] an elevation, partly section, sbowingjc r rename; det s;,- i Figi .i rej3" isfa horizontal section on line 3-3 i V Figure 2,,yiew'ed in the direction ofthe arrows; Figure 4 is 'a vertical sectionon line 44 in Figure '3; Figure Slis a perspective view of a modified apparatus tiedapparatus'jsh own in Figure 5;' a a 9 .s i w Par ssst nm a 11rd r Figure 6 is an elevation, partly in sectiongoffthem As has al- '10 by cyclone separator 15 collection in the receivers.

3 bagfilter system for separating the product particles from the gases; and

Figure 8 is a horizontal section on line 8-8 in Figure 6 showing the entry of the torch burners'through the fur- BR to collect product at the bottom of jacket 10, and

means to take product and gases overhead from jacket with top product recovery means TR.

Insulating jacket 10 is of cylindrical shape several times the height of the furnace F and several times the diameter of fumace F with an upper end portion 11 formed as a frustum of a cone converging to a central opening 12 of circular cross section of considerably less diameter than that of jacket 10. The jacket 10 has a lower end portion 16 formed as an inverted frustum of a cone similar in shape and dimension to upper end por- '18 is a gas-tight valve 21 which can close off conduit 18 :so that product may be collected in the bottom of the 'lower' portion 16 of the jacket 10 during the interval of 'time it takes to open product bin 19 and change product receivers. The bin 19 has a gas-tight door 22 on one side so that product will not be lost during normal product It is important that the height and diameter of the jacket 10 is substantially greater than the respective dimensions of the furnace F to provide a quenching zone 9. In this zone the temperature of the converted feed particles can be cooled so the outer skin of the particle will solidify and achieve the mechanical strength necessary to survive product collection either as overhead from jacket 10 or as fallout in bin 19.

A duct 13 leads from the central opening 12 located in the upper portion of the jacket 10 vertically overhead and makes a long radius turn into a horizontal plane into the opening 14, entering tangentially to the interior of cyclone separator 15. Care should be taken in the duct design to avoid any sharp bends or other obstructions which would cause added turbulence of the gases flowing in duct 13 since many of the newly formed hollow spheres might be ruptured due to the resulting mechanical abrasion.

The cyclone separator may be selected from any of the conventional types of such equipment available in the industry to elfect the separation of'fine particles from gases. In this embodiment the separator 15 is of circular cross section consisting of an upper section of cylindrical shape and a lower portion of inverted frustoconical shape. Another opening 26 in the separator 15 connects to gas outlet duct 25 which communicates tangentially with the interior of separator 15. Duct 25 leads to the inlet 27 of blower 28 powered by an electric motor not illustrated in the drawing. The blower'28 is so mounted as to discharge the gases at a d'e'siredrate from the blower outlet 29 into duct 30 which vents these gases from the building to the outside atmosphere. 'All' the ducts (13, 25,. 30) conveying the hot furnace gases can be constructed of galvanized sheet metal and preferably lagged with insulation. At the bottom'of the lower portion of the separator 15 is a centralopening 31 connected b s aei which. Pa se t fisal vi dqw a a product receiver 34'.

gas-tight door- 35 and in which is situated product receiver 34. A gas-tight valve 36 is disposed within conduit 32 which can close off conduit 32 when the filled product receiver 34 must be removed.

In the practice of this; invention, other conventional systems .for separating fine particles from gases can be successfully substituted for the cyclone separator 15, and such systems are intended to be included as part of the invention. One such system, bag filter B, is shown in Figure 7. The operation of such a system is well known to thoseskilled in the art, and referring to Figure 7 it may be seen that the particle-laden gases enter the bag filter by duct 13. The gases are drawnthrough the bags, leaving the particles as a coating on the outside surface of the bags. The. framessupporting the bags are shaken periodically by a mechanical means whereby the particles are dislodged from the bag surface and fall in the hopper to opening 31. The product collection from this point follows the same procedure as for the cyclone separator system in that opening 31 is connected by conduit 32' to the product recovery bin 33 which contains The gases leave the bag filter B by duct 25, and they are exhausted by the same means employed with the cyclone separator 15 in that duct 25 is connected to a blower not shown in Figure 7 which discharges the gases from the building.

It is also possible to use a cyclone separator system and a bag filter system in combination as an effective means for separating the product particles from the gases.

The feeding mechanism T capable of conveying the feed mixture to the furnace unit F comprises a feed hopper 2 which is a housing of circular cross section having an upper portion of cylindrical shape and a lower portion 3 of inverted frusto-conical shape. This leads to a conduit 4 which leads to a screw conveyor 5 which is powered by an electric motor not illustrated in the drawing. The screw conveyor 5 runs horizontally and supplies feed to a surge box 6. A conduit 7 enters the bottom of the surge box 6 and a conduit 8 leaves the surge box and passes through the jacket 10 and enters centrally into the bottom of furnace F. The suction created by the blower 28 causes air to flow into the conduit 7 which picks up feed material and transports it upwardly through the conduit 8 into the furnace to be described.

Figures 2-4 show in greater detail the components of furnace unit F and the manner in which they coact. The

relative dimensions for these elements depend upon what range of operating conditions are desired for the apparatus. The operating conditions to be considered most determining on the design of these components are gas rate or temperature, the feed rate, and air lift. The housing 38 is generally cylindrical in shape and is formed from ceramic or other fireproof material. Its height is a function primarily of the temperaturerange and air lift anticipated for operation. As the air lift is increased, the height of furnace housing 38 must be increased to provide the same residence time for the particles. It can be readily seen that with the air lift being considered constant, that as temperatures are increased the housing 38 may be shortened so the feed particles will remain in the hot zone of the flame a shorter time and still receive the same quantity of heat. The diameter of housing 38 must be of a practical dimension to accommodate the ranges of feed rate desired for operation, thesupply ofair and gas to develop the temperatures desired, and'the supply of'updraft 'air to cool the wall of the housing 38.

Referring more particularly to Figure 2, the housing 38 for this embodiment is a cylinder opened at its top. Slight departures from a truly cylindrical shape maybe made, such as ellipticallo r conical, and reference herein to'cylindrical in'shape is intended to embrace such slight departures. Spaced equally .around housing 38 are the product recoverf bin '3'3 which is air tight due to the 55 four brackets 37 which supporthou'sin g 35centrallyv'vith in jacket at a position just above the lower end portion 16. Temperature measuring devices are disposedat 48 near thebottom of housing 38 and at 49 near the top of housing 38. with recording mechanism located in some convenient locus away from the apparatus to enable operators to observe temperatures at these two points.

The conduit 8, which transports feed material in a stream of air to the furnace F, enters centrally at the bottom of housing 38. Conduit '39 enters jacket 10 through an opening (Figure 1) and forms a larger conduit 41 surrounding conduit 8. The conduit 39 is open to the atmosphere and air can enter it and the conduit 41 upon operation of the blower 28. A burner 40 surrounds the conduit 41 and is supplied with gas through a conduit 42 which enters jacket 10 through an opening therein (Figure 1) and forms a larger conduit 46 surrounding conduit 41. Conduits 8 and 41 are extended to the same level within furnace F and of such a height so that the finely divided feed material will not melt appreciably before entering the furnace housing 38. The height for both conduits can be as low as the level of burner 40 if the feed rate is sufiiciently high so that particles will not fuse to the burner.

Referring to Figures 3 and 4, burner 40 consists of a circular burner plate immediately surrounding conduit 41 with a plurality of jets on its upper face for the burn-- ing of gas which is transported to the burner by conduits 42 and 46. 'Immediately surrounding the burner 40 is a vcircular plate44, the outer periphery of which forms a seal with the inside of the housing 38. Plate 44 has a, .plurality of holes 45 to supply updraft along thein side 1 of the furnace housing 38 to prevent deposition of product in the melted state on the innerfsurface of furnace housing 38.

The following discussion illustrates how our apparatus 3 may beused. Blower 28 is started and gas line 42 is opened, permitting burner 40 to be fired. Conduits 7 ,and 41 are opened toprovide combustion supporting ,air. Adequate time is allowed ,to build up; a desired temperature in the furnace housing 38, and gas rate is'supplied to burner 40 to maintain this temperature level; Gas rate is balanced with air from conduits 7 and 41tomaintain .a desired temperature gradient between point 48; and point 49 within-the housing38, at which points temperature is being continuously recorded. I

Finely-divided feed mixture of a particle'size range desired is supplied to thefeedvhopper 2, andvthevariquirements of heat'neces'sary tofinitiate fusing in the particle and begin formationof the. desired hollow sphere. As the particles eanven to s'phere'sand arefilled with spherical shape of the particles, the buoyant effect of upward'gases increases and overcomes the former balance between the upward gas, and the force of gravityand carries the particles to a greater. height in the furnace and subsequently out of the furnace into the quenching zone 9 of progressively diminishing temperature, thereby re- 7 moving the particles before they become overheated in the hot regions of the furnace. The residencetime of the particles in the furnace is generally from 0.5 to 10 seconds. The particles in the quenching zone cool below the fusing temperature, thereby solidifying the outer skini able screwconveyor :5 is startedandset at a 'speed to I gas, the relative diameter of the particles increase appreciably; and due to this increase in size and due to the of the particles and providing. the added strength re-= quired by the particles to survive the mechanical abrasion to which they will be subjected during subsequent collection. The particles once in the quenchingizone will be carried to higher levels and eventually suspended in the upward gas flow leaving jacket 10 overhead and transported to cyclone separator 15, or. will stray from the path of upward gases in the quenching zone and be overcome by the forces of gravity so as to settle. to the lower portion 16 of the jacket '10 and fall to'product receiver 20. The particles that, go overhead by duct 13 to separator 15 will move downward to product receiver 34, while the gases will be exhausted to blower 28 and finally vented by duct 30 to the outside atmosphere.

The rate of the blower 28, thefeed screw 5, and the gas to the burner 40 can be adjusted, considering the nature of the feed material andits size so as to give the desired I product. j

Figure 5 describes a modified furnace design also operable within the principle of the updraft method for producing hollow particles, which avoids the requirement for a cooling jacket and permits increased flexibility in design of feed inlet to. the furnace area. Furthermore, this design provides forvall the product removal overhead. The modified furnace design comprises an upright cylindrical housing of uniform diameter consisting of three areas of nearly equal height disposed in vertical sequence as a lower support area, a furnace area, and a quenching area, respectively.

In Figures 5 and 6 the central furnace area 50 is formed by the furnace section 54 which is constructedof insulating firebrick that is capable of sustaining the high temperatures of operation, 'i.e.,.up' to approximately 2500 F. Circle brick is chosen for thi s'sectionso a cylindrical shape can be constructed. The brick is surrounded by a housing 60 Furnace section 54rests on a circular steel plate which has the same inside opening andoutside diameter as furnace section 54. The steel plate 70 is supported by'four steel legs 71 of equal height extending downward to the floor area. The actual height and diameter of furnace section 54 will be dependent again upon the range of operating conditions desired for the apparatus.

Referring now to Figure 8, furnace area 50 is fired directly with six torch burners 51 which enter furnace section 54 on the same plane at a level near the base of the furnace 'area 50 through openings 52 which are spaced equally around furnace section 54. If burners 51 point into the furnace area 50 radially, there 'ma'y be temperature irregularities in the furnace area"50. By adjusting this direction to an angle slightly off the radial position, a spiraling action of the'gases results. which tends to equalize the temperature throughout the furnace area; An angle'jbetween 5 and 10 from the perpendicular will effectively stabilizethe temperature." Referring again to Figure 6, im'mediate'ly above the furnace area 50 a quenching "zone 53 is provided to cool the gases and particles ,before they pass overhead iter separation and product c'ollection. Quenchingzone 53 is formed by the housing 57 and'is va sheet metal cylinder havingnearly'the'same heightas furnace hous'iu'gi60 and having an outsidediamete r' equal to that offu rn ace h ousv ing 60. A flange is provided on the outside periphery I At a position near the lower end of housing 57 a series of air ports 55 are spaced equally around the annular wall of housing 57, and the combined area of these rectangular cross section ports will provide the admittance of sufiicient outside air during operation to maintain a desired temperature within the quenching zone 53. Air

said housing at several points to the steel legs 71.

, :7 1 justing sleeve 56 which'is disposed on housing- 57 vertically above ports 55, and can be lowered to any desired uniform level around the ports within the limits 'of permitting them to be completely open or completely closed. The sleeve 56 can be held in position by the screws 58. The area below the furnace area 50, referred to as the lower support area 65, is surrounded by cylindrical housing 75 composed of sheet metal, similar to housing 57 enclosing the quenching zone 53. The outside diameter of this housing will be equal to the outside diameter of furnace housing 60, and housing 75 will run from immediately below the furnace housing 60 downward to the floor area and will be fixed in place by fastening Near the bottom of housing 75 and spaced equally around the annular wall is a series of airports 76 of rectangular cross section which permit outside air to enter to prevent formation offused material on the walls of furnace area 50 and also to provide combustion supporting gas. The amount of air entering ports 76 during operation. is controlled by sleeve 77 which is positioned'vertically above ports 76 and which fits the outside contour of. housing 75. Sleeve 77,.can be easily lowered to. any desired level, and held by screws 74, thereby restricting the opening of ports 76 as may be required.

Centrally located within the lower support area 65 at a point just below the furnace area 50 is spray nozzle 64 attached to the end of conduit 8 which iscapable of effecting a full cone spray of ,feed solids directly into the furnace area 50. The feed is delivered to the spray .nozzle 64 by the feed system shown generally in'Figure 5 wherein the feed is suspended in air and transported within conduit'8. The structure for adding-the'fee'd particles to the air is similar to that shown intFigurel except that instead of depending upon the blower 28 to draw air through the conduit 7, surge box 6, and conduit 8, a blower 80 is employed to force air and suspended feed through the spray nozzle 64into the furnace area 50.

The method and apparatus of our invention may be used to form hollow spheres from any suitable feed material. The preferred feed materials are those described in co-pending application Serial No. 691,726, filed of even date herewith, the description of the feed materials in that application being incorporated herein by reference to the extent necessary. These materials are composed of a plurality ofingredients which fuse to form a glass and a compound whichliberates a gas at the fusion temperature.

We are aware that apparatus other than thatdescribed may be used to practice the methodof this invention and is the equivalent of that shown.

We claim: a

1. A method of producing hollowspheres from finely divided solid particles of material forming aglass upon fusion thereof in admixture witha'compound which liberates a gas at the temperature of said fusion, which comprises passing a stream of hot gas upwardly through a vertical furnace zone at a temperature to fuse said solid particles and liberate a gas from the said compound, in- (reducing saidsolid particles .in the lower part of said zone so that they are propelled upwardly within said zone said hot gas stream within said zone so that said solid particles remain in the hot gas stream for a period of time necessary to permit fusion and expansion into unitary, hollow spheres, whereby after expansion they are carried upwardly and out of said furnace zone by the said ascending gas stream through a cooling zone, and recovering the spheres so produced.

2. A method of producing hollow spheres from varying sized, finely divided, solid particles of material forming a glass upon fusion thereof in admixture with a compound which liberates a gas at the temperature of said fusion, which comprises passing a stream of hot gas upwardly through a vertical furnace zone at a temperature to fuse said particles and liberate a gas from said compound, in-- troducing said solid particles in the lower part of said zone so that they are propelled upwardly within said zone by said ascending hot gas stream, adjusting the velocity of said hot gas stream within said zone so that the larger of said solid particles remain in the hot gas stream for a longer period of time and the smaller of said solid particles remain in the hot gas stream for a shorter period of time topermit all said particles to fuse and expand into unitary, hollow spheres, whereby after expansion they are carried upwardly and out of said furnace zone by the said ascending gas stream through a cooling area, and recovering the spheres so produced.

3. A method of producing hollow spheres from varying sized, finely divided, solid particles of a plurality of materials forming a glass upon fusion thereof in admixture with a compound which liberates a gas at the temperature of said fusion, which comprises passing a stream of hot gas upwardly through a vertical furnace zone at a temperature to fuse said particles and liberate a gas from said said compound, suspending said solid particles in an air current and introducing said current in the lower part of said zone so that the particles in said curent are propelled upwardly within said zone by said ascending hot gas stream, adjusting the velocity of said hot gas stream within said zone so that the larger of said solid particles remain in the hot gas stream for a longer period of time and the smaller solid particles remain in the hot gas stream for a shorter period of time to permit all said particles to fuse and expand into unitary,'hollow spheres, whereby after expansion they are carried upwardly and out of said furnace zone by the said ascending gas stream through an area in which said stream and said particles are cooled, and recovering from said cooled stream the spheres so produced.

References Cited in the file of this patent UNITED STATES'PATENTS Veatch et al. "June 25, 1957

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2187538 *Aug 11, 1938Jan 16, 1940Amalgamated Minerals CorpMethod of exfoliating vermiculite and similar minerals
US2421902 *Aug 31, 1943Jun 10, 1947Robert NeuschotzMeans of expanding pearlite and like substances
US2430601 *Dec 8, 1941Nov 11, 1947American Aggregate CompanyMethod for treating argillaceous material
US2431884 *Apr 11, 1944Dec 2, 1947Neuschotz RobertMethod of expanding pearlite
US2543987 *Aug 23, 1947Mar 6, 1951Stark Ceramics IncMethod of producing porous, lightweight, burned argillaceous material
US2572484 *Sep 17, 1947Oct 23, 1951HowleApparatus for expanding perlite and the like
US2619776 *Mar 5, 1948Dec 2, 1952Florence R PottersMethod and apparatus for producing small diameter glass beads
US2676892 *Nov 13, 1953Apr 27, 1954Kanium CorpMethod for making unicellular spherulized clay particles and articles and composition thereof
US2797201 *Oct 2, 1953Jun 25, 1957Standard Oil CoProcess of producing hollow particles and resulting product
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3085022 *Jul 11, 1960Apr 9, 1963Heidelberg Portland ZementProcess and apparatus for the production of cement clinker, more especially for white cement
US3097832 *Dec 21, 1960Jul 16, 1963Murdock John BFurnace for expanding perlite and similar substances
US3619306 *Sep 12, 1968Nov 9, 1971Dynamit Nobel AgMolded explosive bodies having variable detonation speeds
US4059423 *Jul 1, 1976Nov 22, 1977Sovitec S.A.Process for the preparation of expansible beads
US4307142 *Aug 8, 1980Dec 22, 1981T.C. Manufacturing Company, Inc.Corrosion-resistant coating composition containing hollow microballoons
US4349456 *Aug 27, 1979Sep 14, 1982Minnesota Mining And Manufacturing CompanyNon-vitreous ceramic metal oxide microcapsules and process for making same
US4441905 *Jan 27, 1983Apr 10, 1984Corning Glass WorksMethod of forming ceramic bodies
US4442175 *Jan 27, 1983Apr 10, 1984Corning Glass WorksCellular ceramic bodies and method making same
US4472185 *Jan 27, 1983Sep 18, 1984Corning Glass WorksMethod of producing a cellular ceramic body
US4475936 *Feb 10, 1983Oct 9, 1984Redland Technology LimitedApparatus for the heat processing of particulate materials
US4487620 *Jun 8, 1983Dec 11, 1984GlaverbelMethod and apparatus for manufacturing rounded vitreous beads
US4643753 *Aug 7, 1985Feb 17, 1987Potters Industries, Inc.Method for making spherical particles
US4659253 *Apr 8, 1985Apr 21, 1987Jacobson Alan RDeep water cable laying method using buoyancy materials
US4677022 *Jan 24, 1986Jun 30, 1987Potters, Industries, Inc.Process for making lightweight body suitable for use as an additive in an article of manufacture, such lightweight body itself, and composite containing same
US5069702 *Dec 20, 1990Dec 3, 1991W. R. Grace & Co.-Conn.Method of making small hollow glass spheres
US5171346 *Jan 22, 1991Dec 15, 1992Aktiebolaget ElectroluxMethod of forming a composite thermal insulating material
US5534348 *Mar 28, 1995Jul 9, 1996Pq CorporationHollow borosilicate microspheres and method of making
US5770416 *Jun 3, 1993Jun 23, 1998Upfront Chromatography A/SPermeable hollow particles having an outer shell of mechanically rigid porous material
US5883029 *May 7, 1997Mar 16, 1999Minnesota Mining And Manufacturing CompanyCompositions comprising fused particulates and methods of making them
US6045913 *Oct 31, 1996Apr 4, 2000Minnesota Mining And Manufacturing CompanyAt least partly fused particulates and methods of making them by flame fusion
US6254981Sep 29, 1999Jul 3, 2001Minnesota Mining & Manufacturing CompanyFused glassy particulates obtained by flame fusion
US7658794Apr 15, 2003Feb 9, 2010James Hardie Technology LimitedFiber cement building materials with low density additives
US7666505Aug 25, 2003Feb 23, 2010James Hardie Technology LimitedSynthetic microspheres comprising aluminosilicate and methods of making same
US7666807Oct 21, 2005Feb 23, 2010Savannah River Nuclear Solutions, LlcHollow porous-wall glass microspheres for hydrogen storage
US7727329Feb 28, 2008Jun 1, 2010James Hardie Technology LimitedFiber cement building materials with low density additives
US7744689Feb 24, 2006Jun 29, 2010James Hardie Technology LimitedAlkali resistant glass compositions
US7878026Aug 25, 2003Feb 1, 2011James Hardie Technology LimitedSynthetic microspheres and methods of making same
US7897534Apr 16, 2009Mar 1, 2011James Hardie Technology LimitedManufacture and use of engineered carbide and nitride composites
US7993570Oct 7, 2003Aug 9, 2011James Hardie Technology LimitedDurable medium-density fibre cement composite
US7998571Jul 11, 2005Aug 16, 2011James Hardie Technology LimitedComposite cement article incorporating a powder coating and methods of making same
US8182606Jun 7, 2010May 22, 2012James Hardie Technology LimitedFiber cement building materials with low density additives
US8603239Apr 25, 2012Dec 10, 2013James Hardie Technology LimitedFiber cement building materials with low density additives
US8609244Dec 8, 2006Dec 17, 2013James Hardie Technology LimitedEngineered low-density heterogeneous microparticles and methods and formulations for producing the microparticles
US8993462Apr 12, 2007Mar 31, 2015James Hardie Technology LimitedSurface sealed reinforced building element
US9222254Mar 12, 2013Dec 29, 2015Schabel Polymer Technology, LlcStructural assembly insulation
US20040079260 *Aug 25, 2003Apr 29, 2004Amlan DattaSynthetic microspheres and methods of making same
US20040080063 *Aug 25, 2003Apr 29, 2004Amlan DattaSynthetic microspheres and methods of making same
US20040081827 *Aug 25, 2003Apr 29, 2004Amlan DattaSynthetic microspheres and methods of making same
US20060059953 *Oct 21, 2005Mar 23, 2006Heung Leung KHollow porous-wall glass microspheres for hydrogen storage
US20060060820 *Sep 21, 2004Mar 23, 2006Schumacher Ray FHollow porous-wall glass microspheres for hydrogen storage
US20060240967 *Feb 24, 2006Oct 26, 2006Hamid HojajiAlkali resistant glass compositions
US20070275335 *May 25, 2006Nov 29, 2007Giang BiscanFurnace for heating particles
US20080096018 *Dec 8, 2006Apr 24, 2008James Hardie International Finance B.V.Engineered low-density heterogeneous microparticles and methods and formulations for producing the microparticles
US20090146108 *Nov 6, 2008Jun 11, 2009Amlan DattaMethods and Formulations for Producing Low Density Products
US20090156385 *Oct 29, 2004Jun 18, 2009Giang BiscanManufacture and use of engineered carbide and nitride composites
US20090200512 *Apr 16, 2009Aug 13, 2009Giang BiscanManufacture and Use of Engineered Carbide and Nitride Composites
US20160221856 *Feb 1, 2016Aug 4, 2016Dennert Poraver GmbhMethod and installation for producing hollow microbeads of glass
EP0046376A1 *Aug 13, 1981Feb 24, 1982Redland Technologies LimitedMethod and apparatus for the production of glass beads
EP0086599A1 *Feb 3, 1983Aug 24, 1983Redland Technologies LimitedMethod and apparatus for the heat processing of particulate materials
EP2516338A2 *Dec 14, 2010Oct 31, 20123M Innovative Properties CompanyMethod for making hollow microspheres
EP2516338A4 *Dec 14, 2010Jul 9, 20143M Innovative Properties CoMethod for making hollow microspheres
WO1987000827A1 *May 21, 1986Feb 12, 1987Potters Industries, Inc.Method and apparatus for making spherical particles, and the particles produced thereby
WO2012126934A1Mar 21, 2012Sep 27, 2012Bayer Materialscience AgMoulded parts consisting of reinforced polyurethane urea elastomers and use thereof
U.S. Classification65/21.4, 23/313.0FB, 23/313.0AS, 65/22, 23/313.00R, 432/61, 264/DIG.600, 432/13, 432/14
International ClassificationC03C11/00, C03B19/10, C04B20/06, C08J9/32, C04B18/02
Cooperative ClassificationY10S264/06, Y10S106/02, C04B18/027, C03B19/107, C03C11/002, C08J9/32, C04B20/066, C03B19/1075, Y10S106/01
European ClassificationC04B20/06F, C08J9/32, C03B19/10C, C03C11/00B, C03B19/10C2, C04B18/02L